JPS6036413B2 - Method for producing 5-membered ring derivative - Google Patents
Method for producing 5-membered ring derivativeInfo
- Publication number
- JPS6036413B2 JPS6036413B2 JP9717877A JP9717877A JPS6036413B2 JP S6036413 B2 JPS6036413 B2 JP S6036413B2 JP 9717877 A JP9717877 A JP 9717877A JP 9717877 A JP9717877 A JP 9717877A JP S6036413 B2 JPS6036413 B2 JP S6036413B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formulas
- reaction
- producing
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- -1 cis-2-butenoic acid ester Chemical class 0.000 description 8
- 101100537937 Caenorhabditis elegans arc-1 gene Proteins 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 244000241257 Cucumis melo Species 0.000 description 2
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
Description
【発明の詳細な説明】 本発明は５員議導体の製造法に関する。[Detailed description of the invention] The present invention relates to a method for manufacturing a five-membered conductor.
本発明の５員誘導体の製造法は以下の通りである。The method for producing the 5-membered derivative of the present invention is as follows.
（式中Ｒ，及びＲ２はそれぞれ低級の直鎖若しくは分枝
状のアルキル基を示す）本発明において出発原料として
用いられる化合＊物【１’は新規な化合物であり、例え
ば以下の様にして合成される。(In the formula, R and R2 each represent a lower straight-chain or branched alkyl group.) The compound * compound [1'] used as a starting material in the present invention is a new compound, for example, as shown below. be synthesized.
（式中Ｒ，，Ｒ２及びＲ３はそれぞれ低級の直鎖若しく
は分枝状のアルキル基を示す）化合物｛４雌例えばフル
フリルァルコールの電解酸化等により容易に得られるシ
ス−２−ブテン酸ェステル誘導体であり、之とアセト酢
酸ェステル‘５１とを縮合させることにより化合物｛６
１が得られる。(In the formula, R, , R2 and R3 each represent a lower linear or branched alkyl group) Compound {4) For example, cis-2-butenoic acid ester easily obtained by electrolytic oxidation of furfuryl alcohol, etc. It is a derivative, and by condensing it with acetoacetate '51, the compound {6
1 is obtained.
化合物■をハロゲン化ベンチニルと反応させると化合物
‘７｝が得られ之を直接或いは加水分解した後に閉環す
ることにより本発明出発原料である化合物‘１｝が得ら
れる。化合物川の化合物【２｝への脱カルボキシレート
化反応は副反応を伴わず、且つ簡便に化合物１｝の５位
にあるカルポキシレート基のみが選択的に除去される。When Compound (1) is reacted with a bentenyl halide, Compound '7' is obtained, and Compound '1', which is the starting material of the present invention, is obtained by ring-closing this directly or after hydrolysis. The decarboxylation reaction of the compound [2} does not involve any side reactions, and only the carboxylate group at the 5-position of the compound 1} is selectively removed.
該反応は溶媒及び触媒の存在下に有利に行なわれる。溶
媒としては例えばベンゼン、トルヱン等の芳香族炭化水
素、テトラハイドロフラン、ジオキサン、エチルエーテ
ル等の脂肪酸エーテル、ｎ−へキサン、ｎ−へブタン等
の脂肪族炭化水素、ジクロルメタン、ジクロルェタン等
のハ。ゲン化炭化水素及び之等の混合溶媒等の不活性溶
媒が用いられる。触媒としては例えばパラトルェンスル
ホン酸、ベンゼンスルホン酸等のスルホン酸、塩酸、硫
酸等の舷酸、ギ酸、酢酸等の有機酸、三弗化ホウ素、塩
化アルミニウム、塩化亜鉛等のルイス酸が使用される。
反応温度は特に限定されないが通常３０〜１２０ｏｏ、
好ましくは６０〜１００ｑｏとするのが良い。上記脱カ
ルボキシレート化反応を例えばジメチルホルムアミド、
ジメチルスルホキシド等の溶媒を用いて、触媒量の食塩
を添加し、反応温度１００〜２００午Ｃ、好ましくは１
３０〜１８０００で行うと、化合物【２’と同時に一般
式（式中Ｒ２は前記に同じ）で表わされる化合物が副生
する。The reaction is advantageously carried out in the presence of a solvent and a catalyst. Examples of the solvent include aromatic hydrocarbons such as benzene and toluene, fatty acid ethers such as tetrahydrofuran, dioxane and ethyl ether, aliphatic hydrocarbons such as n-hexane and n-hebutane, and dichloromethane and dichloroethane. Inert solvents such as mixed solvents of hydrogenated hydrocarbons and the like are used. Examples of catalysts used include sulfonic acids such as para-toluenesulfonic acid and benzenesulfonic acid, ester acids such as hydrochloric acid and sulfuric acid, organic acids such as formic acid and acetic acid, and Lewis acids such as boron trifluoride, aluminum chloride, and zinc chloride. be done.
The reaction temperature is not particularly limited, but is usually 30 to 120 oo,
Preferably it is 60 to 100 qo. The above decarboxylation reaction can be carried out using, for example, dimethylformamide,
A catalytic amount of common salt is added using a solvent such as dimethyl sulfoxide, and the reaction temperature is 100-200 pm, preferably 1 pm.
30 to 18,000, a compound represented by the general formula (wherein R2 is the same as above) is produced as a by-product at the same time as compound [2'.
化合物【２｝の化合物‘３’への還元反応は溶媒及び触
媒の存在下に行うのが好ましい。The reduction reaction of compound [2} to compound '3' is preferably carried out in the presence of a solvent and a catalyst.
使用される溶媒としては例えばメタノール、エタノール
等の脂肪族アルコール、テトラハイドロフラン、エチル
エーテル、ジオキサン等の脂肪族エーテル、ｎーヘキサ
ン、ｎ−へブタン等の脂肪族炭化水素、ベンゼン、トル
ェン等の芳香族炭化水素、アセトン、メチェチルケトン
等の脂肪族ケトン等が挙げられる。触媒としてはパラジ
ウム、白金、ニッケル、ロジウム等の接触還元用触媒が
例示される。触媒の使用量は化合物■に対して通常１〜
２００重量％、好ましくは５〜１０の重量％とするのが
良い。反応は水素下常圧でも或るし、は加圧で行っても
良い。反応温度は特に限定されないが、通常０〜８０℃
、好ましくは１０〜５０ｑｏとするのが良い。以上の方
法により本発明の化合物【２１及び‘３肋得られる。化
合物‘２１及び糊はそれぞれ単離された化合物‘１｝及
び‘２）より得ることもできるが、勿論単離しないで反
応混合物をそのまま原料として使用することによっても
得られる。またそれぞれの化合物は抽出、蒸留、クロマ
トグラフィー、再結晶等の公知の手段により容易に精製
することが可能である。化合物筋はジャスミン様の香気
成分として有用であり、化合物■は上記化合物【３１の
中間体として有用である。Examples of solvents used include aliphatic alcohols such as methanol and ethanol, aliphatic ethers such as tetrahydrofuran, ethyl ether, and dioxane, aliphatic hydrocarbons such as n-hexane and n-hebutane, and aromatics such as benzene and toluene. Examples include group hydrocarbons, acetone, aliphatic ketones such as methethyl ketone, and the like. Examples of the catalyst include catalysts for catalytic reduction such as palladium, platinum, nickel, and rhodium. The amount of catalyst used is usually 1 to 1 per compound ■.
The amount is preferably 200% by weight, preferably 5 to 10% by weight. The reaction may be carried out under hydrogen at normal pressure or under increased pressure. The reaction temperature is not particularly limited, but is usually 0 to 80°C.
, preferably 10 to 50 qo. Compounds [21 and '3] of the present invention can be obtained by the above method. Compound '21 and glue can be obtained from isolated compounds '1} and '2), respectively, but of course they can also be obtained by using the reaction mixture as it is as a raw material without isolation. Further, each compound can be easily purified by known means such as extraction, distillation, chromatography, and recrystallization. Compound 1 is useful as a jasmine-like aroma component, and compound 1 is useful as an intermediate for the above compound [31].
以下本発明の参考例及び実施例を挙げる。Reference examples and examples of the present invention are listed below.
参考例 １
５００叫の反応容器に弗化カリウム４０夕、乾燥にｒｔ
．ーブタノール４０地、シスー４．４ージメトキシ−２
−ブテン酸メチル１２３夕及びアセト酢酸ｔｅｒｔ．ー
ブチルェステル３６夕を入れ、油浴中で２日間蝿梓下１
００ｑｏに加熱する。Reference example 1 Put potassium fluoride in a 500-liter reaction vessel for 40 minutes and dry at RT.
．． -butanol 40%, cis-4.4-dimethoxy-2
-methyl butenoate 123 and acetoacetic acid tert. - Put 36 pieces of butyl ester in it and leave it in an oil bath for 2 days.
Heat to 00qo.
反応終了後ｔｅｎ．ーブタノールを留去する。残笹を酢
酸エチルに溶解し食塩水で洗浄し次いで乾燥する。溶媒
を除去して残造をシリカゲルカラムで精製し、減圧下蒸
留してｂ．ｐ．７２〜７６ｑ０／０．０１４側Ｈｇのメ
チル４−ｔｅｒｔ．ーブトキシカルボニル−３ージメト
キシメチルー５一オキソヘキサノェート〔化合物｛６１
，Ｒ，＝ｔ−Ｂｕ，Ｒ２＝Ｒ３＝ＣＨ８〕を収率９５．
４％で得る。元素分析値Ｃ日
実測値（％） ５６．６５８．１３理
論値（％） ５６．５９８．２３ｍ２
８５１弧‐１（ＣＨ３０）１７３６弧‐１（＞Ｃニ０）
１７１５肌−１（＞Ｃニ。After completion of the reaction, ten. -butanol is distilled off. The remaining bamboo is dissolved in ethyl acetate, washed with brine, and then dried. After removing the solvent, the residue was purified with a silica gel column and distilled under reduced pressure to obtain b. p. 72-76q0/0.014 side Hg methyl 4-tert. -butoxycarbonyl-3-dimethoxymethyl-5-oxohexanoate [compound {61
, R,=t-Bu, R2=R3=CH8] in a yield of 95.
Get it at 4%. Elemental analysis value C day measurement value (%) 56.658.13 theoretical value (%) 56.598.23m2
851 Arc-1 (CH30) 1736 Arc-1 (>C Ni 0) 1715 Skin-1 (>C Ni.
）ＮＭＲ（ＣＣ１４）
１．４３（皮９Ｃ瓜）
３．１９〜３．３８（ｍ６，Ｃ比○）
３．５８〜３．７２（ｍ３Ｃ瓜ＯＣＯ）
３．１９〜３．７２（ｍｌ，ＣＨ）
４．３１（ｔｌ，５Ｈｚ，ＯＣＨＯ）
参考例 ２
反応容器に炭酸カリウム１．斑夕、ョウ化カリウム３０
８脚を入れ、アセトン３０叫とメチル４−ｔｅｒｔ．−
ブトキシカルボニルー３−ジメトキシメチルー５−オキ
ソヘキサノェート４５０の９を溶解したアセトン１０の
‘を加える。) NMR (CC14) 1.43 (skin 9C melon) 3.19-3.38 (m6, C ratio ○) 3.58-3.72 (m3C melon OCO) 3.19-3.72 (ml, CH ) 4.31 (tl, 5Hz, OCHO) Reference Example 2 1. Madarayu, potassium iodide 30
Add 8 terts, 30 ml of acetone and 4-tert. of methyl. −
Add 10 parts of acetone dissolved in 450 parts of butoxycarbonyl-3-dimethoxymethyl-5-oxohexanoate.
次いでベンチニルフロマイド２７０の９を加え、室温下
１時間燈拝し、次いで１３時間７０００で還流する。反
応終了後室温まで冷却し固定分を分離する。減圧下濃縮
し、残澄をシリカゲルカラムで精製して収率９１％でメ
チル４ーアセチル−４一ｔｅｒｔ．ーブトキシカルボニ
ル一３−ジメトキシメチル−６ーノニノェート〔化合物
【７１，Ｒ，＝ｔ−Ｂｕ，Ｒ２＝Ｒ３＝Ｃ比〕を得る。
元素分析値Ｃ日
実測値（％） ６２．５４８．３５理
論値（％） ６２．５０８．３９ＩＲ
２８３７弧‐１（ＣＨ３０）１７２９Ｃの‐１（＞
Ｃニ。Next, Bennylfuromide 270°C was added, heated at room temperature for 1 hour, and then refluxed at 7000°C for 13 hours. After the reaction is completed, the mixture is cooled to room temperature and the fixed component is separated. It was concentrated under reduced pressure, and the residue was purified using a silica gel column to obtain methyl 4-acetyl-4-tert. with a yield of 91%. -butoxycarbonyl-3-dimethoxymethyl-6noninoate [compound [71, R,=t-Bu, R2=R3=C ratio]] is obtained.
Elemental analysis value C day measurement value (%) 62.548.35 theoretical value (%) 62.508.39IR
2837 arc-1 (CH30) 1729C-1 (>
C ni.
）１７１０伽‐１（＞Ｃニ０）
１４３０肌‐１（Ｃは）
１３５４Ｃの一１（ＣＨ３０＞
ＮＭＲ（ＣＣ１４）（６値）
１．１１（斑，ＣＨ３‐Ｃ）
２．２６〜２．５５（２日，ＣＨ２ＣＯＯ）２．５５〜
２．８５（２日，ＣＨ２−Ｃ三）３．６１，６．６５（
細，ＣＨ３０ＣＯ）４‐１８〜４‐３９くＣＨくき）
参考例 ３
メチル４ーアセチル−４−ｔｅ比．ーブトキシカルボニ
ル−３−ジメトキシメチルー６−ノニノエート５４６の
夕をテトラハイドロフラン３０の‘に溶解し、１．５％
週塩素酸水溶液２５Ｍを加えて２８℃で１２時間櫨拝す
る。) 1710 C-1 (> C 0) 1430 Skin-1 (C is) 1354 C-1 (CH30> NMR (CC14) (6 values) 1.11 (spots, CH3-C) 2.26-2. 55 (2nd, CH2COO) 2.55~
2.85 (2 days, CH2-C three) 3.61, 6.65 (
Reference example 3 Methyl 4-acetyl-4-te ratio. -Butoxycarbonyl-3-dimethoxymethyl-6-noninoate (546%) was dissolved in 30% of tetrahydrofuran to give 1.5%
Add 25M aqueous chloric acid solution and incubate at 28°C for 12 hours.
次いで反応溶液を重炭酸ナトリウムで中和し減圧下濃縮
する。銭溝を酢酸エチルで抽出し、乾燥後濃縮してメチ
ル４ーアセチルー４一ｔｅれ．ーブトキシカルボニル−
３−ホルミル−６ーノニノェート〔化合物【８’，Ｒ，
＝ｔ一Ｂｕ，Ｒ２＝ＣＨ３〕を得る。粗収率９８％。Ｎ
ＭＲ（ＣＣ１４）９．６５（ＣＨＯ）
ＩＲ（ｎｅａｔ） ２８４１肌‐１（ＣＨ。The reaction solution is then neutralized with sodium bicarbonate and concentrated under reduced pressure. Extract the Qianmizo with ethyl acetate, dry and concentrate to extract methyl 4-acetyl-4-te. -butoxycarbonyl-
3-formyl-6 noninoate [compound [8', R,
=t-Bu, R2=CH3] is obtained. Crude yield 98%. N
MR (CC14) 9.65 (CHO) IR (neat) 2841 Skin-1 (CH.
）１７３３ １７１６弧‐１（＞Ｃニ。）上記で得られ
た化合物■の７９０戊９を酢酸１の‘、ピベリジソ１机
【を含むベンゼン５０机上に溶解し４時間還流する。) 1733 1716 arc-1 (>Cd.) 790 9 of compound (1) obtained above was dissolved in 50 ml of benzene containing 1 part of acetic acid and 1 part of piberidiso, and refluxed for 4 hours.
反応終了後、溶媒を除去し残澄を酢酸エチルに溶解する
。水、重炭酸ナトリウム水で洗浄後乾燥する。残澄を減
圧下蒸留すると５−ね【ｔ．ーブトキシカルボニル一４
ーメトキシカルボニルメチル−５一（２−ベンチニル−
２ーシクロベンテノン〔化合物‘１１，Ｒ，＝ｔ−Ｂｕ
，Ｒ２＝ＣＨ３〕を得る。ｂ．ｐ．８２〜８６ｑｏ／０
．００６肋Ｈｇ、収率７８％。元素分析値
Ｃ日
実測値（％） ６７．３６７．７０理
論値（％） ６７．４８７．５５ＮＭ
Ｒ（ＣＣ１４）１．０２（ｔ３，Ｃ比）
１．３７（広９，Ｃ馬）
１．７６〜２．７３（ｍ．６，ＣＨ２Ｃ＝Ｃ，ＣＨ２Ｃ
Ｏ）３．３３〜３．５８（ｍ．１，ＣＨ）３．６６（ｓ
３，ＣＨ３０）
６．１０（ｄｄｌ，５ＨＺ，２Ｈｚ，Ｃ＝ＣＨＣＯ）７
．５０（ｄｄｌ，５日２，２ＨＺ，ＨＣ＝ＣＣＯ）参考
例 ４メチル４−アセチル−４ーメトキシカルボニル−
３ージメトキシメチルー６ーノニノエート５３０の９を
テトラハイドロフラン２０の【‘こ溶解し、１％週塩素
酸水溶液２５泌を加えて２６〜２８午０で１幼時間鷹拝
する。After the reaction is complete, the solvent is removed and the residue is dissolved in ethyl acetate. Wash with water and sodium bicarbonate and dry. When the residue is distilled under reduced pressure, 5-t. -butoxycarbonyl-4
-Methoxycarbonylmethyl-5-(2-benbenyl-
2-cyclobentenone [Compound '11, R, = t-Bu
, R2=CH3]. b. p. 82-86qo/0
．． 006 rib Hg, yield 78%. Elemental analysis value C day actual value (%) 67.367.70 theoretical value (%) 67.487.55NM
R (CC14) 1.02 (t3, C ratio) 1.37 (wide 9, C horse) 1.76-2.73 (m.6, CH2C=C, CH2C
O) 3.33-3.58 (m.1, CH) 3.66 (s
3, CH30) 6.10 (ddl, 5Hz, 2Hz, C=CHCO)7
．． 50 (ddl, 5 days 2,2HZ, HC=CCO) Reference example 4-methyl 4-acetyl-4-methoxycarbonyl-
Dissolve 530 parts of 3-dimethoxymethyl-6noninoate in 20 parts of tetrahydrofuran, add 25 parts of a 1% aqueous solution of chloric acid, and boil for 1 hour from 26 to 28 p.m.
次いで反応溶液を重炭酸ナトリウムで中和し減圧下濃縮
する。残澄を酢酸エチルで抽出し、乾燥後濃縮してメチ
ル４−アセチル−４ーメトキシカルポニル−３−ホルミ
ル−６ーノニノエート〔化合物（８｝，Ｒ，＝Ｒ２＝Ｃ
比〕を得る。収率９８．３％。ＮＭＲ（ＣＣ１４）
９．６５（ＣＨＯ）
ＩＲ２８４１弧‐１（ＣＨ。The reaction solution is then neutralized with sodium bicarbonate and concentrated under reduced pressure. The residue was extracted with ethyl acetate, dried and concentrated to give methyl 4-acetyl-4-methoxycarponyl-3-formyl-6 noninoate [compound (8}, R,=R2=C
ratio]. Yield 98.3%. NMR (CC14) 9.65 (CHO) IR2841 Arc-1 (CH.
）１７３３，１７１＆か‐１（＞Ｃ＝０）
上記で得られた化合物脚の５００の‘を酢酸１の‘、ピ
ベリジン１の‘を含むベンゼン２００の【に溶解し６時
間還流する。) 1733,171&ka-1 (>C=0) 500' of the compound leg obtained above is dissolved in 200' of benzene containing 1' of acetic acid and 1' of piverizine, and refluxed for 6 hours.
反応終了後、溶媒を除去し残澄を酢酸エチルに溶解する
。１０％塩酸、重炭酸ナトリウム水で洗浄後乾燥する。After the reaction is complete, the solvent is removed and the residue is dissolved in ethyl acetate. Wash with 10% hydrochloric acid and sodium bicarbonate and dry.
濃縮後残澄をシリカゲルカラムで精製すると５ーメトキ
シカルボニル−４ーメトキシカルボニル−５一（２ーベ
ンチニル）−２ーシクロベンテノン〔化合物‘１｝，Ｒ
．＝Ｒ２＝ＣＨ３〕を収率８１％で得る。ｂ．ｐ．１１
０〜１１？０／０．１５肋Ｈｇ。元素分析値
Ｃ日
実測値（％） ６４．６４６．３０理
論値（％） ６４．７４６．５２ＮＭ
Ｒ（ＣＣ１４）１．０５（ｔ．３，ＣＨ３）
１．８０〜２．３０（ｍ．２，Ｃ比Ｃ：Ｃ）２．３４〜
２．８６（ｍ．４，ＣＨ２Ｃ＝Ｃ，ＣＱＣＯ）３．６１
，３．６７（公．６，ＣＨ３０）６．１４（ｄｄ．１，
細２，汎２，Ｃ＝ＣＨＣＯ）７．５９（ｄｄ．１，６Ｈ
Ｚ，２ＨＺ，ＨＣ＝ＣＣＯ）実施例 １５−ｔｅ九．一
ブトキシカルボニルー４ーメトキシカルボニル一５−（
２ーベンチニル）一２ーシクロベンテノン８００の９ヲ
５０の上のベンゼンに溶解し、ｐ−トルェンスルホン酸
３０の９を添加して３０分間還流する。After concentration, the residue was purified with a silica gel column to yield 5-methoxycarbonyl-4-methoxycarbonyl-5-(2-bentenyl)-2-cyclobentenone [Compound '1}, R
．． =R2=CH3] with a yield of 81%. b. p. 11
0-11?0/0.15 rib Hg. Elemental analysis value C day actual value (%) 64.646.30 theoretical value (%) 64.746.52NM
R (CC14) 1.05 (t.3, CH3) 1.80~2.30 (m.2, C ratio C:C) 2.34~
2.86 (m.4, CH2C=C, CQCO) 3.61
, 3.67 (public.6, CH30) 6.14 (dd.1,
Fine 2, Pan 2, C=CHCO) 7.59 (dd. 1, 6H
Z, 2HZ, HC=CCO) Example 15-te9. monobutoxycarbonyl-4-methoxycarbonyl-5-(
Dissolve 800 parts (9 parts of 2-bentenyl)-2-cyclobentenone in 50 parts of benzene, add 9 parts of p-toluenesulfonic acid (30 parts), and reflux for 30 minutes.
反応後車炭酸ナトリウムで中和し溶媒を除去する。残澄
をシリカゲルカラムで精製し、減圧下蒸留して４−メト
キシカルボニルメチル−５一（２−ベンチニル）２ーシ
クロベンテノン〔化合物ｔ２｝，Ｒ２＝ＣＨ３〕を得る
。ｂ．ｐ．１０２〜１０３００／３肋Ｈｇ，収率９３％
。ｍ ２２３０弧‐１（Ｃ三Ｃ）
ＮＭＲ（ＣＤＣ１３）
１．０６（ｔ．７，２ＨＺ，細，ＣＨ３）１．４４〜３
．０２ｍ，１が）
３．７０（ｓ．斑，ＣＨ３０）
実施例 ２
５一（２ーベンチニルー４ーメトキシカルボルメチル６
２−シクロベンテノン６００の９とパラジウム−炭素触
媒１．２夕をメタノール５０の‘に入れ、室温，１気圧
の水素下で１時間蝿拝する。After the reaction, neutralize with sodium carbonate and remove the solvent. The residue is purified with a silica gel column and distilled under reduced pressure to obtain 4-methoxycarbonylmethyl-5-(2-bentenyl)2-cyclobentenone [compound t2}, R2=CH3]. b. p. 102-10300/3 Hg, yield 93%
. m 2230 arc-1 (C3C) NMR (CDC13) 1.06 (t.7, 2HZ, thin, CH3) 1.44-3
．． 02m, 1) 3.70 (s. spot, CH30) Example 2 5-(2-benchinyl-4-methoxycarbomethyl 6
600 parts of 2-cyclobentenone and 1.2 parts of the palladium-carbon catalyst were placed in 50 parts of methanol and stirred at room temperature under 1 atm of hydrogen for 1 hour.
水素を除去し触媒を炉別する。濃縮後残澄をシリカゲル
カラムで精製し、減圧蒸留すると２−ｎーベンチルー３
ーメトキシカルボニルメチルーシクロベンタノン〔化合
物糊，Ｒ２＝ＣＨ３〕を得る。収率９８％、ｂ，ｐ，１
０９〜１１ぞＣ／〇，２柳Ｈｇ。元素分析値Ｃ日Remove hydrogen and separate the catalyst. After concentration, the residue was purified using a silica gel column and distilled under reduced pressure to obtain 2-n-benzene 3
-Methoxycarbonylmethyl-cyclobentanone [compound paste, R2=CH3] is obtained. Yield 98%, b, p, 1
09~11zo C/〇, 2 Willow Hg. Elemental analysis value C day
Claims (1)
は分枝状のアルキル基を示す）で表わされる化合物を脱
カルボキシレート化して一般式▲数式、化学式、表等が
あります▼ （式中Ｒ＿２は上記に同じ）で表わされる化合物を得
て、次いで之を環元することを特徴とする一般式▲数式
、化学式、表等があります▼ （式中Ｒ＿２は上記に同じ）で表わされる５員環境誘
導体の製造法。[Claims] 1. Decarboxylate a compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 each represent a lower linear or branched alkyl group) General formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ General formulas characterized by obtaining a compound represented by (in the formula, R_2 is the same as above) and then converting it into a ring element ▲ Numerical formulas, chemical formulas, tables, etc. There is a method for producing a 5-membered environmental derivative represented by ▼ (in the formula, R_2 is the same as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9717877A JPS6036413B2 (en) | 1977-08-12 | 1977-08-12 | Method for producing 5-membered ring derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9717877A JPS6036413B2 (en) | 1977-08-12 | 1977-08-12 | Method for producing 5-membered ring derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5432449A JPS5432449A (en) | 1979-03-09 |
| JPS6036413B2 true JPS6036413B2 (en) | 1985-08-20 |
Family
ID=14185322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9717877A Expired JPS6036413B2 (en) | 1977-08-12 | 1977-08-12 | Method for producing 5-membered ring derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6036413B2 (en) |
-
1977
- 1977-08-12 JP JP9717877A patent/JPS6036413B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5432449A (en) | 1979-03-09 |
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